Treatment of polychloro copper phthalocyanine



y 6, 195 H. l. STRYKER ETAL 2,833,782

TREATMENT OF PQLYCHLORO CQPPER PHTHALOCYANINE Filed April 12, 1954 INVENTORS 22 9:. 2:25 u I l I I I lntensiiy relative to highest peak) HARVEY STRYKER ADDISON H. WILLIAMSON PETER F. GROSS TREATMENT or rorvenrono corrER PH'lHALOCYANlNE Application April 12, 1954, Serial'No. 422,492 a 15 Claims. (Cl. 260-6145) This invention relates to a process :forthe treatment of crude polychloro copper phthalocyanine whereby to obtain the color in a finely divided physical form having good pigmentery properties such .as tinctorial strength, of ness an i e omfrornzg it- Y v hlore coppe phthaleey nine in practic gen r y refers to copper phthalocya me which has been chloria e to ry .n ari'ts mtheoretical chlorine conn Th max m m theeretlcal content is 16 Cl atoms per molecule, or a chlorine analysis of-50.;% byiweight. This ideal, however, is seldom realized in practice, and the m h c s marily employed in ommercial *mflnufacture generally introduce a m f hlo i e (on 1 aver g p r molecul Aci e y n th s app a on. th itermrp'olychlero c pp rh l eyen ne shall h understood asreferrin :1 a

co h in chlo ne analysis-efn tless than'46.0-%-,

h c o r ponds o 113-5 Q1 atoms per molecule.

Several methods have been developed -,in th art for hl rina in copp phtha ocyanin :to the high Stage above referred to. ne :of {these reacts chlorine -with pp r ph oeyan ne wh le h latteris dissolved in a e o Va i able ne anic flux, orin t nc ailow-meiltg m tur of luminumhlor dean dium chloride (U. S. P. 2,247,752). The ratio.oflthese is generally in the vicinity of the eutectic ratio, that is 4:1 byweight, in h der na d; the efore, t i :p e s using an alumin m-ch r d so ium-chlorid melt wil h inafter be spoken of as the eutectic process, and the -pigment.gobrai d ther f om l be refe red to as'eu ec i crude.

is in n io .is conce ned pr. ily with jpel ch pp r ph hel cyan n asebtained inthis s -cal ed ute t p e sss appl c le. howev r, ls to :crudes obta ne by other p oce s s h ein th colqrcom sin contact with sub an al q nt es f alumi um chl ride i g or af er chlori a on- ?[h in ention has OI its p mary obje t a method of tr atmen the crude reacon m s whe eby to obt in th olor directly n a r mentary form. By this wemeen' that the coloris obined i t e .form of an aque s :raste o a-sott, dry powder wh h i adap e d rec y for inco p t n into qui rg ic hicles to p oduc pa nt varnish s r printing inks. ,Another object of this invention is to achieve the aforegoing .pigmentary state with maximum economy and Without resort to any treatments with conntra s liurie a id, chlorosiilioni acid, or e he t ong ds. Var ou additional bje ts andeehi v m nts of this invention will become apparent as the description p o e d I In the mentioned 'eutecticprocess' for the commercial production of polychloro copper 'phthalocyanine, the crude color, after drowning in water, filtering, washing and drying, is obtained in the form of line particles which, however-Jack in tinctorial strength; To be suitable for incorporation into paints, varnishes and inks, the color musthave a so-called pigmentary form or texture. This implies "fine particles, which disperse readily in oil, which are free of grit, and which develop maximum tinctorial from about 13.5 to :about 1.5.5

United States Patent 0 'phthalocyauine into pigmentary state.

2,833,782 ,{iP fs l e M y 19 8 strength, when incorporated-into an inkor paint-vehicle,

with a minimum of mechanical working. (The latter property isgenerallyreferred to-as softness.) I .In'the' cas'eof many pigments, especially copper phthalocyanine and metal-free phthalocyanine a prevalent :method for converting the crude color into'pigmentary form has been the so-called acid-pasting'metho'd. This term implies dissolving the color in concentrated sulfuric acid and then drowning ithe solution in water, whereby the color precipitates .in very fine, crystalline form and is filtered .oif. Numerous modifications of and improvevAmong other :metho'ds :recentl-y suggested for the phthalocyanines .in general, and especially for unchlorinated copper pihthalocyanine, are the -so-called acid- ;sluliry processes. In the :basic process of this type, -sul furic acid of lower concentration is employed/so that it isinF apable of Ldissolv'ing'the color, but-has some sort of swelling action thereon, most proba'bly' throu-gh conversion of ,thepigmentinto a sulfate (British'l503 ,6'6'6 and .FItATjreport 1313, vol. sI'II, pages 298-303)? Aniinproved modification of this basic process which makes it applicable to polychloro .copper :p'hthalocyanine is set forth in the copending application of George Barnhar-t, Serial No. 278,969 (Patent.No..2,765,'3l9, issued October 2, 1956), wherein the acid-slurrying is achieved by using sulfuric acid of 9899% strength, but'in conjunction with sodium sulfate which apparently forms some inorganic complex compound with the acid-and promotes the de- 2,402,167), solvent-milling .(U. S. .P. 2556,7264 and salt-.solventmilling (U. S.-.-P. 2,556,728.).

Now according to this .invention,a generallyapplicabl practical, economical and uniformly reliable method has been developed for converting icrude p'olychloro-copper For *the sake of simplifying the presentation, the discussion -hereinbelow will be limited at first to "the crude polyc'liloro product obtained in the eutectic process.

In its principal features our novel method comprises treating the reaction mass, directly as obtained in the eutectic process, with water and an organic liquid in such a manner as to effect simultaneously or in sequence, .in either order, the following two achievements: '(ll) Separation of the inorganic constituents of the reaction mass by dissolving ,them in water; (2 coating the pigment particles, completely or partially, with an organic liquid. Following these two principal achievements, the mass on hand may'be treated in any convenient manner to obtain it in any desired commercial form. For instance, the mass may be filtered to eliminate excess water, and then handled in commerce as a paste containing both .water and organic solvent. Or the filtered mass may be steam distilled, filtered oil and washed to give apurelyaqueous paste. Or again, the mass may 'besteam distilled, .filtered 0E, washed and dried to .give a dry product. Various detail hereinbelo'w.

containing thedesired organic liquid, followed by filtra tion. Or it may be achieved .by drowning the crude melt in water, and then adding an organic liquid. Or again,

The organic liquid contemplated for use in our invention is one which is immiscible with water and which will normally displace water '1 from .the surface of a solid 'the organic liquid may be entered into the molten eutectic mass prior to drowning in water.

phthalocyanine pigment particle. In other words, the' organic liquid is one which is adapted for flushing a phthalocyanine pigment, for instance copper phthalocyanine,= out of anaqueous mass thereof. As illustrations of effective liquids. may be mentioned toluene, xylene, p-chlorotoluene, o-dichlorobenzene, trichlorobenzene, n'itrobenzene, o-nitrotoluene, mineral spirits, trichloroethylene, tetrachloroethylene, cetane, pineoil, benzonitrile, dimethyl aniline, quinoline and n-amyl. acetate. Where it is decided to add the organic liquid to ,the molten eutectic mass prior-to drowning, it is obviously desirable to choose a liquid which boils above the temperature of I the molten mass, It is also desirable that; the liquid be volatile with steam, ,so as to be capable of removal by steam distillatiomxif desired.

4 by weight for each estimated part of pigment in the filter cake; in other words, the organic liquid is taken in quantity suflicient to produce with the pigment a free-flowing slurry, but avoiding excessive quantities which would needlessly increase the cost of the process. The suspended mass is heated, with good agitation, at a temperature between 102 C. and 170 C. for a period of time sufficient to insure evaporation of all moisture from the mass. In the case of organic liquids which boil below 100 C., the temperature of heating may be as low as the boiling point of the liquid in question.

In the third step of said procedure, the excess organic liquid from the second step is removed either by filtering off, followed by washing ofthe pigment .with a volatile, water-miscible organic solvent, for instance alcohol, or by steam distillation. The end product is customarily obtained in the form of an aqueous paste, suitable directly for handling in commerce or in paint or ink manufacture. But it mayalso be dried to give a soft powder of pigmentaryv qualities I I Now, while the above detailed procedure is still considered good and gives a product of highest pigmentary qualities,f'we now find nevertheless that our invention is not restricted to such meticulous detail of.procedure, and

that a product of excellent physical qualities may also be obtained by omitting or consolidating some of the above The quantity of water should of course be suflicient to dissolve-the inorganic constituents of the reaction mass, but will normally be several times this quantity. The

,quantity'of organic liquid should be sufficient to effect flushing,v of thepigment particles, without forming a continuous organic phase.

(4) (As an optional step)-production of an aqueous press cake, which is suitable either for direct use by the paint or printing ink manufacturers or for drying to produce a soft;powder.

According to the further description in said copending application, the first stepis achievedby drowning the eutectic. reaction mass in water which contains or to which is subsequently added an organic liquid such as o-dichlorobenzene in quantity-corresponding to from 0.4

This point is discussed in further steps of procedure, thereby increasing theeconomy of the entire process. r

According to our further development of this invention, we find that we may omit steps 2 and 3 altogether. Thus the filtered and washed product from the first step may be handled in commerce or paint manufacture as an aqueous paste of pigment having some organicsolvent therein, and characterized by superior pigmentary qualities compared to material produced by acid pasting, as m'ore'fully discussed below.

We may, however, also suspend the filtered and washed product of step 1 in a fresh quantity of water, and then proceed to steam distil off the solvent as in step 3 above. The resulting aqueous paste may be used as such or it may be dried. Or again, the filtering and washing operations may be carried out after steam distillation. In such cases, the excess aqueous phase may be decanted off, whereupon alkali is added to neutralize the acidity of the residual paste, and steam distillation is applied followed eventually by filtering oil. the pigment and washing.

We also find that our novel process is not limited to the use of polychloro copper phtha-locyanine crudes obtained to 1.1 parts by. weight per part of polychloro copper phthalocyanine present .in the reaction mass. The mass is stirred at moderate temperature (25 to 40 C., and in any event not above 80* C.), and the undissolved color is filtered ofland washed with water. Operating in this manner the inorganic salts are more .efiectively removed in the washing operation, WhenTan organic liquid is not employed in the drowned mass, it is virtually impossible to remove the inorganic salts completely by ordinary washing of the filter cake with water, no matter how prolonged the washing. p Inthe next step of our earlier procedure, the washed pigment from step 1 is heated in a relatively large quantity. of a water-immiscible, neutral, organic liquid which can be readily removed by steam distillation- Suitable illustrations for this purpose are. the ,benzenoid hydrocarbons and their nuclear halogenand nitro derivatives, for instance benzene, toluene, xylene, monochlorobenzene, odichlorobenzene, trichlorobenzene, nitrobenzene, o-nitrotoluene and p-chlorotoluene. Conveniently, the

liquid chosen here will be the same as that used in step in the eutectic process but may also be applied to other products wherein the polychloro product is produced in the presence of substantial quantities of aluminum chloride, say 2 or more'moles ofAlCl per mole of initial pigment. Such a process, for instance, is the modified sulfur-dichloride process of chlorination described and claimed in copending application of F. F. Ehrich Serial No. 422,674, of even date herewith. Finally, we find that the required contact above mentioned is not limited to aluminum chloride, but may be achieved also with aluminum bromide and ferric chloride, all of which come under the general formula MX wherein X stands forchlorine or bromine, while M des- 'ign'ates the metals Al and Fe.

The quantities of organic liquid employed in the various steps may also be varied considerably from the teach- 'ings in our said prior application.

In those processes which involve drowning 'in water,

results in the case of manyliquids (e. .g. xylene); however, to insure uniformly good results in all cases we recommend, as a thumb rule, a of'0.40 part of the organic liquid per part of pigment. I

In processes which do not involve filtration prior to removal of the organic liquid, for instance where treatment with organic liquid is followed directly by alkalization and steam distillation, there is no upper limit to the quantity of organic liquid useable, except of course the practical consideration of cost.

In all the treatments above,our product is obtained in a novel physical form which differs in crystal habit from poychloro copper phth-alocyanine obtained by the hitherto known methods. The unique crystal habit of our product can be distinguished from other polychlor'o copper phthalocyanines' by certain physical measurements described below.

We find all the products treated according to this invention to be distinctly more yellow in their green shade than-samples of the same polychloro material which have undergone acid-pasting. Our products are frequently also i of jetter masstone than the acid pasted material, and at least equal to it in brilliance (sometimes referred to as intensity).

Electron micrographs show our novel product to consist of uniform crystals of parallelepiped shape, of a length which is from 2 to 3 times the width and from 5 to times the thickness. The length itself is in the range of-0.05 to 0.2 micron.

Another means of defining the physical properties of our novel product is by its X-ray diffraction pattern. The use of this technique to characterize crystal phases is well known, and the various phases may be recognized by the presence or absence of characteristic interplanar spacings within the crystal as exemplified by the peaks in the X- ray diffraction record. However, it is also recognized that variations in crystals not involving changes in crystal phase may influence the relative intensity of the X-ray diffraction peaks and we have selected the relative intensities of two prominent peaks as one of the distinguishing characteristics of the new product.

-'It is an accepted rule in the study of X-ray diffraction patterns of very small crystals that the width of the diffraction peaks is a measure of crystal size with the broad er peaks accompanying the smaller crystal sizes. It has been observed that the products of this invention exhibit characteristically narrow X-ray diffraction peaks and we have selected the width of one prominent peak as another characteristic of these products.

For a better understanding of the discussion on this "topic, reference is made to theaccornpanying drawing, wherein the sole figure represents two-typical X-ray patterns obtained in the study of our novel products.

The solid curve represents the products of this invention; the dotted curve represents the products obtained from the same crude polychlo'ro materials but refined through the old, acid-pasting procedure. Both are idealized curves in the sense that in transcribing them from the original pattern recorded by the Geiger-counter apparatus, the extremely Wriggly oscillations superimposed upon the principal curve by the random background noise have been ignored.

The patterns shown in the drawing were obtained through the well-known powder technique using a North American Philips X-ray difiractometer. The radiation was that known as copper K06. run at 35,000 volts and 18 milliamperes. The slit system used 1 divergence slits and a 0.003 inch receiving slit at a distance of 170 mm. from the specimen. The intensity of the diifracted beam was recorded by means of a Geiger counter and plotted against the Bragg angle (20).

In all X-ray diffraction patterns of polychloro copper phthalocyanine, there is a peak of maximum intensity at a Bragg angle of approximately 26.7. For purposes The X-ray tube was :6 of defining the new product, the intensity of the peak at Bragg angle 28.5 is? measured relative to thefintensity of said maximum peak, and the peak at Bragg. angle 6.l' is measured for width as an index to average "crystal size. It is our unexpected discovery that all. polychloro cop per phthalocyanine products which have been chlorinated in the presence of aluminum chloride, or treated with relatively large amounts of a metal halide of form MX as above. defined, yield X-ray patterns "under the "conditions described, in which the intensity of the peak at Bragg angle 285 is less than 40% of that at 26.7". When these products are finished by the prior art method of acid pasting or similar methods in which particle size reduction is brought about through chemical changes and regeneration, the intensity of this peak approaches and sometimes reaches zero. On the other hand, in the case of the new products of this invention, the intensity of this peak at 28.5 is found to fall in the narrow range of 18% to 40% of that of the peak at 26.7. In estimating this degree of. intensity, the measurement is made from a base line which excludes the background scattering of the X-ray beam and, in this case, is drawn between the two points on the curve which correspond to Bragg angles 30 and 21, these representing low points on-the curve of each sideof the maximum peak.

It is also accepted that the width of an X-ray diffraction peak at its half-maximum intensity is a function of the crystallite size. Using the peak at 6:1" under the conditions described above, the highly crystalline products of this invention give patterns in which the horizontal width at half-maximum intensity, measured from the base line drawn between the two points on-the curve corresponding to Bragg angles 7.3 and 5, is less than 0.5 (on the Bragg angle scale). All prior-art, acidpasted products show a peak width under these conditions in the order of 0.7 to 0.9. A few highly crystalline products have been observed with peak Widths of about 0.3'which were made by processes not using large amounts of AlCl in the chlorination but they-show an intensity in the 28.5", peak markedly exceeding 40%.

To summarize, a detailed procedure for characterizing the new product by X-ray ditfraction is as follows:

(1) Obtain an X-ray diifraction pattern, plotting intensity against Bragg angle.

(2) Draw a base line through the two points on the curve corresponding to Bragg angles of 30 and- 21, and again between the two points corresponding to Bragg angles 7.3" to 5.0.

(3) Determined peak intensities by measuring peak height from the base-line at 26.7, 28.5 and. 6.l. Express the peak intensities relative to the intensity at 261, calling the latter I (4) Measure the horizontal width of the band at the half-maximum intensity for the peak at 6.1.

Returning now to the details of our process, the same may be modifiedin various ways as long as it contains the essential treatments hereinabove set forth. For instance, during the steam distillation step, where suchstep is employed, certain reagents may be added to effect additional improvements in the quality of the product. Thus, maintaining the mass on the alkaline side(pH 7) has been found to give products of highest-tiuctorialstrength. Addition of minor quantities (say about 2% based on weight of pigment) of oxidizing agents, for instance .SQ- dium chromate or sodium nitrite, exerts a beneficial effect upon the brilliance of the color. Addition of minor quantities (about 2%) of fatty compounds such as natural fats, long-chain fatty acids, soaps or esters, or long-chain fatty alcohols or their esters (acetates, propionates, etc.) contributes toward the production of soft powders.

In the other steps, too, certain modifications of procedure are permissible. Thus, while drowning thecrude chlorination mass directly in water containing theorganic liquid (or to which the organic liquid is subsequently added) obviously entails the minimumlabor of water until free from acid and i: materials, it is nevertheless entirely permissible of the aqueous mass by repeated decantations, by continuous filtration, or by other convenient physical P a 1 The steam distillation step, where used, may be achieved any convenient apparatus. We find, however, that removal of theorganic phase may be achieved most efficiently and economicallyby using an apparatus adapted for turbannular flow and-passing in the steam at a veloc- ,ity; adapted to produce the turbannular state (see for instance, Morrow and Parsons, U. S. P. 2,467,769, or

.Roberts, Gage and B rautcheck, U..S. P. 2,528,320).

Without limitingour invention, the following examples are given to illustrate our preferred mode of operation.

I Parts mentioned are by weight.

. EXitM i Step 1.-350 amelt obtained by chlorinating 53 partsof copper. phthalocyanine in an anhydrous aluminum chloride-sodium chloride melt according to U. S. P. 2,247,752. until. 49 partsof chlorine have been absorbed were drowned in 1600 parts of cold water. The temperature having risen to 78 C., 450 parts. of ice were fed in to cool the mass. to about 40 C. 65 parts of o-dichlorobenzene were then stirred in during 10-15 minutes. The o-dichlorobenzene was completely adsorbed onto the particles .of the pigment, so that no oily phase v separated.

The slurry was filtered and the cake was washed with from water-soluble chlorides.

Step 2.The filter cake was added to 650 parts of o-dichlorobenzene and agitated to form a smooth slurry. This was heated to l00-102 C. and held until the water originally present in the filter cake was boiled off, along with a fraction of the o-dichlorobenzene. The temperaturelof the dewatered slurry was thenraised to 130135 C. andheld for 1.5 hours.

' Step 3.The slurry was cooled to below 90 C. and 8 parts of sodium hydroxide were added as a concentrated aqueous solution. Live steam was introduced into the bottom of the slurry and the o-dichlorobenzene was steam distilled off until the distillate coming over contained no appreciable amount of o-dichlorobenzene. The slurry was then filtered and the cake was washed with water until free from alkali.

When a portion of the filter cake was flushed into lithographic varnish it was found to. be'yellower, stronger,

and jetter in masstone than polychloro copper phthalocyanine presscake prepared by acid pasting in a mixture of sulfuric and chlorosulfonic acids.

When a portion of the filter cake was dried, pulverized,

and ground into lithographic varnish, it was found to be yellower, brighter, of equal tinctorial strength and jetter in masstone compared to polychloro copper phthalocyanine powder prepared by acid pasting.

The procedure of thisexample was repeated, except that a solution of 0.6 part of beef tallow in 32 parts of o-dichlorobenzene was added to the mass in step 3 prior to alkalization and steam distillation. The results were essentially the same as those obtained above.

EXAMPLE 2 A series ofruns were made as in Example 1, except (a) Monochlorobenzene, 55 and 550 parts.

(b) .Trichlorobenzene,j72 5116720 parts.

(a) p-Chloro'toluene, and'640 parts. (d) o-Nitrotoluene, 65 and 650 parts. An improved product (compared to acid pasted, material) was obtained in each instance. EXAMPLE 3 Turbann ular steam distillation (a) To a dewatered slurry of 100 pounds of polychloro copper phth'alocyanine in 770 pounds of o-dichlorobenzene, prepared by the procedure of Example 1, steps 1 andZ, were added 2 pounds of oleic acid. The resulting slurry .was pumped at the rate of 17.5 pounds per hour into one end of aSO-foot tube having an inside diameter 0f-0.'8 inch.,,.Simultaneously, a solution of 6.4

pounds of sodium hydroxide in 27.5 pounds of water was dripped in, uniformly (over the entire 50-hour period), at theintake side of the pump. Steam, ,at' a pressureof 26 pounds gauge was introduced into the intake end of the tube at the rate of 310 pounds per hour. During the concurrent passage through the tube,

V the o-dichlorobenzene was vaporized by the steam. The

mixture of vapor, steam and water-wet color passed from the tube into a cyclone separator. v From the bottom of this, the aqueous slurry of color was discharged continuously, while the mixture of steam and o-dichlorobenzene vapors waspassed into a condenser. The slurry of color was filtered and washed with water until free from alkali. p

A portion of the filter cake was flushed into lithographic varnish.- It was found to be substantially free from grit, to have good tinctorialstrength and to be jetter and yellower than'polychloro copper phthalocyanine press cake prepared by the acid-pasting finishingmethod.

A second portion of the filter cake was dried, pulverized and ground into lithographic varnish on an ink mill. The product had a soft texture, developing its full tinctorial strength without excessive milling. Compared with polychloro copper phthalocyanine powder prepared by acid pasting, it was jetter, yellower, brighter and stronger.

(b) The process of part (a) of this example was modified whereby the slurry of pigment and solvent was pumped into the turbannular still at the rate of 131 pounds per hour and the solution of sodium hydroxide was replaced by a solution of 8.5 pounds of sodium carbonate in pounds of Water. The isolated pigment was subjected to the same tests and gave similar results. a

(c) When the process of the preceding paragraph was modified by replacing the solution of sodium carbonate with a solution of 6.4. pounds of sodium hydroxide and 2.0 pounds of sodium nitrite in 27.5 pounds of water,

similar results were obtained.

EXAMPLE 4 Modified drowning procedure o-dichlorobenzene and agitated to form a smooth slurry.

The slurry was heated to l00-l02 C., until all water boiled off, then the dewatered slurry was raised to l35 C., and held for 1.5 hours.

Step 3.The slurry was cooled to below 90 C., and 2 parts of polytitanyl stearate (Balthis, U. S. 2,621,194), 2 parts of sodium chromate and 15.8 parts of sodium allowed to settle.

"thewater originally present in the cake/was A "6111 along with a'iraction of the o-dichlorobenzene fllhe carbonate were added. The o-dichlorobenzene was then .removedby steam'distillatiou. lT'ne slu'rry wa's 'filtere'd and washed with water until free from alkali.

.W'heu subjected to'tests as in theprecedin'g examples,

water, were'ad'ded to 660 partsof water and agitated to a smoothslurry while warming to '50 "C. 6 1'parts of odichlorobenzene were added to the'agitated slurry during one-halfh'our. The agitation was shut oif and the solid color particles with "adsorbed o-diehlorobe'nzene were The :clear aqueouslayer was decanted and replaced with an'equal volume-of fresh "cold water. Live steam was introduced into the bottom of'the vessel to agitate and heat the mixture Steam was shut off when the temperature reached 65 C.; the color was allowed to settle and the, =aqueouslay'er was again decanted. Thiswashing by decantationwas repeated twice more. tion with dilute caustic (3 ,parts of sodium hydroxide Then the material was washed o'nceihydecantadissolved in 500 parts of water).

S't'ep "2. -'6l0 parts of o-diclilorobenzene were added, the temperature was raised to'1'00-102? 'C., and held at that point until the remaining water'wa's boiled bit, together with a portion of the o-diehmrobenzene; The

dewatered slurry was heated "for 1.5 hours at12'5- 132 C., then cooled to below90" C. and placed in a steam still. 7

Step 3.- TA solution of 8 parts of sodium hydroxide "andl parts of sodium chromatecrystals in IZO-patts of water was added, and live steam was blown intothe lower part of the vessel until all "the 'o-di'chlorob'enzene had been distilled out. The aqueous slurry'wasfiltered, washed free from water-soluble material, dried and ,pulverized. A portion of the owder was ground into alkyd resin enamel. it was found to be yellower, brighter and stronger than acid-pasted polychlo'ro copper plithalocyau'in'e powder.

EXAMFLE 6 Two additional runs were made accordingto' procedure of Example "5, except that "the 61 and 610 parts of o-dichlorobenzene therein'mentioned were replaced by the following liquids in the following quantities respectively.

(a) Nitrobenzene, 60 and 600 parts. 7 Xylene, 44 and 440 parts.

' The results were essentiallythe-s'ame as in' 'Example '5.

' EXAMPLE 7 3.25 .parts of -o-dichlorobenzene were added over .a

period or minutes to an aqueous .slurry containing 500 ,parts of polychlor-o copper phthalocyanine which slurry was obtained by drowning n eutectic chlorination mass prepared by the process :desc'nibed .in step 1 of Example 1. The o-dichlorobeniene was completelyadsorbed on the particleso'fpolychloro copper.,phtha1o- 'cya'nine. The ,slurry 'was,.filtered .and thecake was Washed with water until free from water solubleachlorides. The color cake, was reslurried .for .2.hours at of sodium hydroxide ,had been added as .a concentrated parts of Q dichlorObenZene and agitated to form. a smooth slurry. This was heated to 1001-102" C., and held until boiled steam distillation.

slurry was then heated to -135 C. for Zhours',

cooled: to room temperature, and addedto 1,-690 parts-of o-di'chlorobenzene. A concentrated, aqueous solution containing 35.5 parts of sodium nitrite and 3515 parts of sodium hydroxide was added during the removal of the o-dichlorobenz'ene by turbannular steam distillation as described in Example 3. The aqueous color slurry was "made acidicto litmus paper with concentrated aqueous phosphoric acid and agitated for one-half hour. The slurry was filtered and the filter cake was washed with water until free from acid. 7

A sample of the "filter'cake was flushed intolithographic varnish and was found to be yellower, brighter, of equal tinctorial strength and jetter in masstone compared to polychloro copper phthalocyanine press cake prepared by acid-pasting.

A 'sample'of the filter cake'wasdried, pulverized and when subjected tothe same test, gave similar-results.

EXAMPLE 8 Simplified procedure 227 parts of odichlorobenzene were added during '15 minuteswith agitation to an aqueous slurry containing 325 parts of polychloro'co'pper phthalocyanine, which slurry was obtained by drowning a eutectic chlorination mass that had been prepared according to the method described in step 1 of Example 1. The o-dichlorobenzene was completely adsorbed on the particles of p'olychlo'ro copper phthalocyanine. The-slurrywas filtered and the filter cake was washed with water until free from acid and water-soluble chlorides.

The filter cake thus obtained, when flushed into lithographic varnish gave jet, strong and bright resultsin the usual ink drawdown-tests.

In an alternative procedure,the above filter cake was dried at 100 C. to give a powder which was found to'be satisfactory for use in alkyd resin enamels.

' According to a second alternative, the above filter cake was added to 1000 parts of water which contained 8 parts of sodium-hydroxide and the 'slurry was agitated for 2 hours at 100 C. The slurry was'then filtered and adjusted to apH of 8 by addition of monosodium phosphate. 2parts of sperm oil and -6 parts of sodium nitrite were addedandthe o-dichlorobenzene was removed by The slurry was filtered and the filter cakewashed "with Water until free from alkalinity. A portionof the filter cake was dried, pulverized andground 'in'to lithographic varnish and was found to be yellowe'r, brighter, of equal tinctorial strength and jetter in mass'to'ne "compared to .polychloro copper phthalocyanine prepared by acid-pasting.

When the above example was repeated except for replacing the 227 parts of o-dichloroben'zene by parts of xylene, essentially sirnilarresults were obtained.

EXAMPLE 9' 200 parts of copper phthalocyanine were chlorinated to a chlorine content of about 46% by heating under pressure with sulfur dichloride in the presence of antimony chloride as the catalyst after the teachings of Fox and Johnson in U. S. 2,377,685. When chlorination was complete, the charge was vented to atmospheric pressure and 'cooledto about 100 C.v Then, 200 parts of anhydrous aluminum chloride were added to the charge and :the .sulfur chloride was removed by distillation in the ,presence of a stream of chlorine gas. The dry powder acts.

of the sulfur dichloride.

then slurriedin parts of water and 240 part s of o-dichlorobenzene were added over a period of about 30 minutes .while stirring vigorously. The granular slurry spe' rm oil were then added, the o-dichlorobenzene removedby steam distillation and the aqueous slurry filtered, washed and dried as in Example (b). The rewasfiltered and washed free of chlorides. The granular cake was then introduced into a steam still containing 4800 parts of water in which were dissolved 150 parts of trisodium phosphate (Na PO .12H,O) and 8 parts of sperm oil were added. The o-dichlorobenzene was removed by steam distillation and the resulting alkaline slurry was filtered hot, washedfree of alkali, dried at 60 C. and pulverized to give a polychloro copper phthalocyanine having excellent pigmentary qualities.

EXAMPLE 10 Product from modified SCl process perature of about 180 C. During this heating cyclethe pressure increased because of the vapor pressure of the 'sulfur dichloride and because of the HCl released during chlorination of the phthalocyanine molecule. When the pressure reached 265 p. 5. i. g. (pounds per square inch gauge) it was then vented and kept at 265 p. s. i. g. throughout the cycle which extended for about 4 hours after the temperature reached 180 C. The temperature was maintained at 180l85 C.

At the end of the 4-hour heating cycle, the pressure p in the autoclave was reduced to atmospheric pressure by venting through a recovery system for the sulfur chloride and heating was continued while a stream of chlorine gas was passed through to assist in the removal and recovery A dry product was obtained which required further treatment before use as a pigment.

When the aluminum chloride in part (a) of this example was replaced by 327 parts of anhydrous ferric chloride the results obtained were essentially the same.

(b) 182 parts of the crude'pigment obtained above (containing 122 parts of water-extracted solids) were slurried in 2000 parts of water with good agitation and the stirring was. continued for about minutes until a smooth slurry resulted. I Then 79 parts of o-dichlorobenzene were added dropwise while continuing the vigorous agitation to give granular pigment particles which i were filtered from the water and washed until free of chlorides. Thegranular cakewas then chargedrtoa steam still containing 2000 parts of water in which 50 parts of disodium phosphate (Na,HPO .12H O) were dissolved.

2.4 parts of sperm oil were added and the o-dichlorobenzene removed by steam distillation.- The resulting alkaline slurry was filtered hot, washed free of alkali, dried at 60 Q1 and pulverized to give. a high strength polychloro copper phthalocyanine which required no further treatment for use as a green pigment. Furthermore, this pigmentkwas markedly more yellow in hue than a portion of thesame crude pigment which had been extractedin the heretofore known manner and conditioned forpigment use either by acid pasting or by the milling methods of Lane and Stratton (U. S. 2,556,727) or of Graham (U. S. 2,556,728 and 2,556,730).

EXAMPLE 11 182 parts of the crude pigment of Example 10(a) were slurried with water, treated with 79 partsof o-dichlorobenzene, filtered and washed as in Example 10(b) above. The granular cake was then charged to a steam still containing 2000 parts of water and while vigorously stirring,

parts of o-dichlorobenzene were added. 50 parts of disodium phosphate (Na,HPO .12H,O) and 2.4 parts of sulting product after pulverization is a bright green pigment which exhibits excellent color strength and a yellower hue than the pigment of Example 10(b). Both of these products exhibit jet masstone in printing ink and a highly desirable two-tone etfect when combined with flake aluminum in the pigmentation of automotive lacquers or enamels.

EXAMPLE 12 EXAMPLE l3 Caustic treatment before granulation 182 parts of the crude pigment of Example 10(a) (about 122 parts of water extracted solids) were slurried in about 2000 parts of water with good agitation until a smooth slurry was obtained. This slurry was heated to the boil, stirred for 1 hour at the boil then filtered and washed free'of soluble salts. The filter cake was then added to a solution of 10 parts NaOH in 2000 parts of water." This slurry was treated with 122 parts of o-dichlorobenzene and 4 parts stearic acid, and the mixture was subjected to steam distillation until all of the o-dichlorobenzene was removed. The slurry was finally filtered, washed alkali free and dried to give a strong, bright, green pigment of yellow hue. This pigment was excellently adapted for ease of dispersion in the vehicles normally used in the trade.

We claim as our invention:

1. A process of recovering pigmentary polychloro copper phthalocyanine from an anhydrous reaction mass containing non-pigmentary polychloro copper phthalocyanine in admixture with a metal halide of the group consisting of aluminum chloride, aluminum bromide and ferric chloride, the proportion of metal halide to pigment being not less than 2:1 in moles, which comprises contacting said reaction mass with water and with an inert, waterimmiscible, organic diluent which is capable of displacing water from the surface of a solid phthalocyanine pigment particle, the proportion of said organic liquid to pigment being not less than 0.3:1 by weight, whereby to form an aqueous solution of said metal halide, and separating the pigment from said aqueous solution.

2. A process as in claim .1, wherein said anhydrous admixture is the crude reaction mass obtained by chlorinating copper phthalocyanine in a melt of sodium chloride and aluminum chloride.

3. A process as in claim 2 wherein said anhydrous reaction massis contacted directly with a mixture of water and said organic liquid.

4. A process as in claim 2 wherein the said crude reaction mass is first drowned in water, then filtered off and entered into a mixture of water and said organic liquid...

5.-A process as in claim 1, wherein the aqueous pigment paste obtained at the end of the process defined in said claim is treated further to remove the organic liquid.

6. A process as in claim 1, wherein the aqueous pigment paste obtained at the end of the process defined in said claim is subjected to steam distillation to remove the organicliquid.

to produce a pigment powder.

8. A process as in claim 1, wherein the aqeuous pigment paste obtained at the end of the process defined in said claim is first diluted with an added quantity of organic liquid, suificient to produce a continuous phase thereof, whereupon the mass is heated to drive ofi its water content.

9. The process of recovering polychloro copper phthalocyanine from the reaction mass obtained in the aluminum chloride-sodium chloride fusion process of chlorinating copper phthalocyanine, which comprises in combination a sequence of the following steps: (1) cffecting separation of the pigment from inorganic salts by the aid of an aqueous drowning bath containing a waterimmiscible organic liquid in quantity not less than 40% and not exceeding 110% by weight based on the weight of pigment in the reaction mass, (2) transferring the water-wet pigment into a continuous organic liquid phase which is immiscible with water, accompanied by complete elimination of the residual water, and (3) removing the organic liquid phase from the system formed in step 2 and replacing the same by a continuous aqueous phase, to produce an aqueous paste of the pigment.

10. A process as in claim 9, wherein the organic liquid employed in step 1 is a benzenoid compound selected from the group consisting of the benzenoid hydrocarbons and their nuclear halogen and nitro derivatives.

11. A process as in claim 9, wherein step 2 is achieved by stirring the water-wet pigment obtained in step 1 in a water-immiscible organic liquid boiling above 100 C., said liquid being employed in quantity from 5.5 to 9 parts by weight based on the dry weight of pigment, and maintaining the mass at a temperature above C., whereby to effect complete dewatering of the mass.

by steam distillation in the presence of alkali.

13. A process as in claim 9, wherein step 3 is achieved by steam distillation in the presence of alkali and in the further presence of a fatty substance selected from the group consisting of fats, soaps, long-chain fatty acids, long-chain aliphatic alcohols, esters of such fatty acids and esters of such alcohols.

14. A process as in claim 9, wherein step 3 is achieved by steam distillation in the presence of alkali and in the further presence of an oxidizing agent selected from the group consisting of sodium chromate and sodium nitrite.

15. As a new composition of matter, a tinctorially strong, crystalline, polychloro copper phthalocyanine containing at least 46% chlorine and being further characterized by consisting predominantly of parallelepiped shaped particles of 0.05 to 0.2 micron length, said length being 2 m3 times the width and 5 to 10 times the thickness, and by exhibiting a bright, yellow-green hue when tested in lithographic ink drawdowns, said composition of matter being the product resulting from the process defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,049 Vesce Nov. 29, 1938 2,282,006 Sloan May 5, 1942 2,291,452 Dahlen et al July 28, 1942 2,305,379 Detrick et al. Dec. 15, 1942 2,359,737 Lacey et al Oct. 10, 1944 2,549,842 Moser Apr. 24, 1951 2,615,027 Bluemmel et a1 Oct. 21, 1952 2,618,642 Keller et al. Nov. 18, 1952 2,645,643 Gottlieb July 14, 1953 

1. A PROCESS OF RECOVERING PIGMENTARY POLYCHLORO COPPER PHTHALOCYANINE FROM AN ANHYDROUS REACTION MASS CONTAINING NON-PIGMENTARY POLYCHLORO COPER PHTHALOVYANINE IN ADMIXTURE WITH A METAL HALIDE OF THE GROUP CONSISTING OF ALUMINUM CHLORIDE, ALUMINUM BROMIDE AND FERRIC CHLORIDE, THE ROPORTION OF METAL HALIDE TO PIGMENT BEING NOT LESS THAN 2:1 IN MOLES, WHICH COMPRISES CONTACTING SAID REACTION MASS WITH WATER AND WITH AN INERT, WATER-IMMISCIBLE, ORGANIC DILUENT WHICH IS CAPABLE OF CYANINE PIGMENT PARTICLE, THE PROPORTION OF SAID ORGANIC CYANINE PIGMENT PARTICLE, THE PROPORTION OF SAID ORGANIC LIQUID TO PIGMENT BEING NOT LESS THAN 0.3:1 BY WEIGHT, WHEREBY TO FORM AN AQUEOUS SOLUTION O F SAID METAL HALIDE, AND SEPARATING THE PIGMENT FROM SAID AQUEOUS SOLUTION. 